CA2717887C - Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors - Google Patents
Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors Download PDFInfo
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- CA2717887C CA2717887C CA2717887A CA2717887A CA2717887C CA 2717887 C CA2717887 C CA 2717887C CA 2717887 A CA2717887 A CA 2717887A CA 2717887 A CA2717887 A CA 2717887A CA 2717887 C CA2717887 C CA 2717887C
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- iron
- electrochemical process
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 356
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 164
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 157
- 238000000034 method Methods 0.000 title claims abstract description 103
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 64
- 238000011084 recovery Methods 0.000 title claims abstract description 12
- 239000002699 waste material Substances 0.000 title abstract description 13
- 238000005554 pickling Methods 0.000 title description 13
- 238000005065 mining Methods 0.000 title description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 68
- 239000002184 metal Substances 0.000 claims abstract description 66
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 150000001450 anions Chemical class 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 38
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- -1 platinum group metals Chemical class 0.000 claims description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 15
- 238000002386 leaching Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 235000011149 sulphuric acid Nutrition 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- 239000003011 anion exchange membrane Substances 0.000 claims description 11
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 229910052718 tin Inorganic materials 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 229910000978 Pb alloy Inorganic materials 0.000 claims description 7
- 239000003014 ion exchange membrane Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 6
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001093 Zr alloy Inorganic materials 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- 238000005341 cation exchange Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 229910052758 niobium Inorganic materials 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 239000003870 refractory metal Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 229910000497 Amalgam Inorganic materials 0.000 claims description 4
- 229910001020 Au alloy Inorganic materials 0.000 claims description 4
- 229910000925 Cd alloy Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 239000003353 gold alloy Substances 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 3
- 229910001245 Sb alloy Inorganic materials 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002140 antimony alloy Substances 0.000 claims description 3
- 239000003575 carbonaceous material Substances 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001029 Hf alloy Inorganic materials 0.000 claims description 2
- 229910001362 Ta alloys Inorganic materials 0.000 claims description 2
- 229910000756 V alloy Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 2
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 2
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- HFLAMWCKUFHSAZ-UHFFFAOYSA-N niobium dioxide Inorganic materials O=[Nb]=O HFLAMWCKUFHSAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims 2
- 229910010293 ceramic material Inorganic materials 0.000 claims 2
- 229910001316 Ag alloy Inorganic materials 0.000 claims 1
- 229910001252 Pd alloy Inorganic materials 0.000 claims 1
- 229910004160 TaO2 Inorganic materials 0.000 claims 1
- NQKXFODBPINZFK-UHFFFAOYSA-N dioxotantalum Chemical compound O=[Ta]=O NQKXFODBPINZFK-UHFFFAOYSA-N 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 239000011241 protective layer Substances 0.000 claims 1
- 229910052596 spinel Inorganic materials 0.000 claims 1
- 239000011029 spinel Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 54
- 238000005868 electrolysis reaction Methods 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 229910001868 water Inorganic materials 0.000 description 27
- 238000004519 manufacturing process Methods 0.000 description 16
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 15
- 229910000831 Steel Inorganic materials 0.000 description 12
- 239000010959 steel Substances 0.000 description 12
- 239000010406 cathode material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 8
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical class [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000004277 Ferrous carbonate Substances 0.000 description 7
- 150000001768 cations Chemical class 0.000 description 7
- 235000019268 ferrous carbonate Nutrition 0.000 description 7
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002893 slag Substances 0.000 description 7
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 5
- 238000003487 electrochemical reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 239000002659 electrodeposit Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical compound [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-N peroxydisulfuric acid Chemical compound OS(=O)(=O)OOS(O)(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-N 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 235000011151 potassium sulphates Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- DAFQZPUISLXFBF-UHFFFAOYSA-N tetraoxathiolane 5,5-dioxide Chemical compound O=S1(=O)OOOO1 DAFQZPUISLXFBF-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920002466 Dynel Polymers 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
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- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 235000013980 iron oxide Nutrition 0.000 description 1
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 229910052603 melanterite Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000135 prohibitive effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/36—Regeneration of waste pickling liquors
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/20—Electroplating: Baths therefor from solutions of iron
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/045—Leaching using electrochemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US4428208P | 2008-04-11 | 2008-04-11 | |
| US61/044,282 | 2008-04-11 | ||
| PCT/CA2009/000471 WO2009124393A1 (en) | 2008-04-11 | 2009-04-14 | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2717887A1 CA2717887A1 (en) | 2009-10-15 |
| CA2717887C true CA2717887C (en) | 2016-06-14 |
Family
ID=41161495
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2717887A Active CA2717887C (en) | 2008-04-11 | 2009-04-14 | Electrochemical process for the recovery of metallic iron and sulfuric acid values from iron-rich sulfate wastes, mining residues and pickling liquors |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US20110089045A1 (es) |
| EP (1) | EP2268852B1 (es) |
| JP (1) | JP5469157B2 (es) |
| CN (1) | CN102084034B (es) |
| AU (1) | AU2009235914A1 (es) |
| BR (1) | BRPI0911653B1 (es) |
| CA (1) | CA2717887C (es) |
| ES (1) | ES2712722T3 (es) |
| SI (1) | SI2268852T1 (es) |
| WO (1) | WO2009124393A1 (es) |
| ZA (1) | ZA201007214B (es) |
Families Citing this family (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5100573B2 (ja) * | 2008-08-27 | 2012-12-19 | 株式会社オメガ | 電極構造 |
| EP2625316A2 (en) * | 2010-10-07 | 2013-08-14 | Ceramatec, Inc | Chemical systems and methods for operating an electrochemical cell with an acidic anolyte |
| WO2013022020A1 (ja) * | 2011-08-10 | 2013-02-14 | 住友電気工業株式会社 | 元素回収方法および元素回収装置 |
| US20130233720A1 (en) * | 2011-10-27 | 2013-09-12 | Gagik Martoyan | Extraction of metals |
| WO2013080326A1 (ja) * | 2011-11-30 | 2013-06-06 | 不二商事株式会社 | めっき液の再生方法 |
| CN102839396B (zh) * | 2012-09-27 | 2016-05-25 | 兰州交通大学 | 一种用于金属氯化物精炼的膜电积槽 |
| US9695050B2 (en) | 2012-11-02 | 2017-07-04 | Terra Co2 Technologies Ltd. | Methods and systems using electrochemical cells for processing metal sulfate compounds from mine waste and sequestering CO2 |
| CN103866344B (zh) * | 2014-03-11 | 2016-05-18 | 中国环境科学研究院 | 一种电解制备硝酸的方法 |
| KR101528507B1 (ko) * | 2015-01-13 | 2015-06-12 | 한국지질자원연구원 | 리튬계 전지로부터 코발트 및 망간의 동시 회수 방법 |
| JP6428441B2 (ja) * | 2015-03-31 | 2018-11-28 | 栗田工業株式会社 | 酸廃液の処理装置及び処理方法 |
| WO2016159051A1 (ja) * | 2015-03-31 | 2016-10-06 | 栗田工業株式会社 | 金属イオン含有酸液の処理方法及び処理装置 |
| JP6428440B2 (ja) * | 2015-03-31 | 2018-11-28 | 栗田工業株式会社 | 鉄族金属イオン含有液の処理方法及び処理装置 |
| CN106757174B (zh) * | 2017-02-23 | 2020-08-21 | 黄芃 | 一种电沉积制备金属粉末的方法 |
| KR102227226B1 (ko) * | 2017-12-15 | 2021-03-11 | 도야마 스미토모 덴코우 가부시키가이샤 | 금속 다공체의 제조 방법 및, 도금 처리 장치 |
| CN109231556A (zh) * | 2018-10-16 | 2019-01-18 | 合肥工业大学 | 酸/碱废液的扩散渗析处理装置及其处理方法 |
| CN109628953B (zh) * | 2018-12-26 | 2020-10-23 | 浙江工业大学 | 一种铜电解液中去除砷锑铋的方法 |
| CN109848172A (zh) * | 2018-12-26 | 2019-06-07 | 安徽万纬工程管理有限责任公司 | 一种石油化工废弃物处理方法 |
| EP4219801A1 (en) | 2019-01-24 | 2023-08-02 | Atotech Deutschland GmbH & Co. KG | Membrane anode system for electrolytic zinc-nickel alloy deposition |
| CN110079837B (zh) * | 2019-04-24 | 2020-10-13 | 北京科技大学 | 水溶性氟盐体系熔盐电解可溶性钛酸盐制备金属钛的方法 |
| CN110306044B (zh) * | 2019-07-18 | 2020-05-19 | 北京科技大学 | 一种水热草酸络合浸出钒铁尖晶石含钒矿物中钒的方法 |
| EP3825441A1 (en) * | 2019-11-21 | 2021-05-26 | COVENTYA S.p.A. | An electrolytic treatment device for preparing plastic parts to be metallized and a method for etching plastic parts |
| CN111118544A (zh) * | 2020-01-17 | 2020-05-08 | 厦门欣赛科技有限公司 | 一种含铁酸性废液的处理方法 |
| EP3875643A3 (en) * | 2020-03-04 | 2021-12-08 | AT & S Austria Technologie & Systemtechnik Aktiengesellschaft | A method of processing an etching waste medium from circuit board and/or substrate manufacture |
| CN111663039B (zh) * | 2020-06-01 | 2022-07-12 | 中国恩菲工程技术有限公司 | 多金属结核的回收方法及装置 |
| CN113003669B (zh) * | 2021-02-25 | 2022-06-28 | 哈尔滨工业大学 | 一种用于电催化氧化废水处理的氟修饰亚氧化钛活性膜电极的制备方法及穿流式水处理模式 |
| TWI823276B (zh) * | 2021-03-02 | 2023-11-21 | 奧地利商奧特斯奧地利科技與系統技術有限公司 | 一種處理來自電路板和／或基板製造的蝕刻廢棄物介質之方法 |
| BR112023019059A2 (pt) * | 2021-03-24 | 2023-10-17 | Electrasteel Inc | Remoção de impurezas em um sistema de conversão de ferro |
| CN113371799B (zh) * | 2021-06-22 | 2022-10-04 | 哈尔滨工业大学 | 基于单线态氧的电化学消毒方法 |
| CN113788520A (zh) * | 2021-10-08 | 2021-12-14 | 北京首钢吉泰安新材料有限公司 | 一种铁铬铝酸洗的工艺及废水处理方法和废水处理装置 |
| CN113787085A (zh) * | 2021-10-14 | 2021-12-14 | 中钢集团马鞍山矿山研究总院股份有限公司 | 一种提取电炉除尘灰中Fe、Zn、Pb并高值化利用的方法 |
| WO2023118925A1 (en) * | 2021-12-20 | 2023-06-29 | Arcelormittal | Method for manufacturing iron metal by electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US992951A (en) * | 1909-10-23 | 1911-05-23 | Franz Fischer | Process for the manufacture of ductile electrolytic iron. |
| US984703A (en) * | 1910-07-14 | 1911-02-21 | Nat Tube Co | Process of making sulfuric acid and electrolytic iron. |
| GB191028226A (en) | 1910-12-05 | 1911-09-28 | Sherard Osborn Cowper-Coles | An Improvement Process for the Production of Iron by Electro-deposition. |
| US1954664A (en) * | 1932-10-24 | 1934-04-10 | John R Cain | Electrolytic process for the regeneration of pickle liquor |
| US2653905A (en) * | 1947-12-06 | 1953-09-29 | Pyror Ltd | Process for total treatment of copper-containing iron pyrites |
| US2810686A (en) * | 1954-11-09 | 1957-10-22 | Rohm & Haas | Electrolytic treatment of waste sulfate pickle liquor |
| JPS4621089B1 (es) * | 1968-02-13 | 1971-06-15 | ||
| JPS4936847B1 (es) * | 1970-12-25 | 1974-10-03 | ||
| US4060464A (en) * | 1974-06-26 | 1977-11-29 | Boliden Aktiebolag | Method for extracting and recovering iron and nickel in metallic form |
| US4113588A (en) | 1976-03-09 | 1978-09-12 | Solex Research Corporation Of Japan | Process for recovery of waste H2 SO4 and HCl |
| US5227032A (en) * | 1991-09-24 | 1993-07-13 | The United State Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Method for producing oxygen from lunar materials |
| DE4218915A1 (de) * | 1992-06-10 | 1993-12-16 | Heraeus Elektrochemie | Verfahren und Vorrichtung zur Regenerierung einer Metallionen und Schwefelsäure enthaltenden wäßrigen Lösung sowie Verwendung |
| DE4326854A1 (de) * | 1993-08-11 | 1995-02-16 | Heraeus Elektrochemie | Verfahren zur Regenerierung einer Metallionen und Schwefelsäure enthaltenden wässrigen Lösung sowie Vorrchtung |
| FR2823195B1 (fr) | 2001-04-09 | 2004-07-02 | Electricite De France | Regeneration par extraction liquide-liquide des acides a partir de solution aqueuse contenant des metaux |
| CA2392846C (en) * | 2002-07-09 | 2008-07-15 | Hatch Associates Ltd. | Recovery and re-use of anode oxygen from electrolytic cells |
| US7790016B2 (en) * | 2005-04-05 | 2010-09-07 | King Fahd University Of Petroleum And Minerals | Integrated electrolytic-electrodialytic apparatus and process for recovering metals from metal ion-containing waste streams |
| WO2008034212A1 (en) * | 2006-09-21 | 2008-03-27 | Qit-Fer & Titane Inc. | Electrochemical process for the recovery of metallic iron and chlorine values from iron-rich metal chloride wastes |
-
2009
- 2009-04-14 SI SI200931934T patent/SI2268852T1/sl unknown
- 2009-04-14 WO PCT/CA2009/000471 patent/WO2009124393A1/en active Application Filing
- 2009-04-14 JP JP2011503319A patent/JP5469157B2/ja not_active Expired - Fee Related
- 2009-04-14 US US12/921,522 patent/US20110089045A1/en not_active Abandoned
- 2009-04-14 EP EP09730372.1A patent/EP2268852B1/en active Active
- 2009-04-14 CN CN2009801221140A patent/CN102084034B/zh active Active
- 2009-04-14 CA CA2717887A patent/CA2717887C/en active Active
- 2009-04-14 ES ES09730372T patent/ES2712722T3/es active Active
- 2009-04-14 BR BRPI0911653-2A patent/BRPI0911653B1/pt active IP Right Grant
- 2009-04-14 AU AU2009235914A patent/AU2009235914A1/en not_active Abandoned
-
2010
- 2010-10-08 ZA ZA2010/07214A patent/ZA201007214B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| US20110089045A1 (en) | 2011-04-21 |
| EP2268852A4 (en) | 2011-07-06 |
| ES2712722T3 (es) | 2019-05-14 |
| JP5469157B2 (ja) | 2014-04-09 |
| WO2009124393A1 (en) | 2009-10-15 |
| JP2011516730A (ja) | 2011-05-26 |
| AU2009235914A1 (en) | 2009-10-15 |
| CA2717887A1 (en) | 2009-10-15 |
| BRPI0911653A2 (pt) | 2015-10-13 |
| CN102084034B (zh) | 2012-12-12 |
| ZA201007214B (en) | 2011-08-31 |
| EP2268852B1 (en) | 2018-12-05 |
| SI2268852T1 (sl) | 2019-09-30 |
| EP2268852A1 (en) | 2011-01-05 |
| BRPI0911653B1 (pt) | 2019-07-30 |
| CN102084034A (zh) | 2011-06-01 |
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